JPH07325373A - Photographic element - Google Patents

Abstract

PURPOSE: To provide the photographic element incorporating a coupler exhibiting good sensitometric response even in the case of low developability. CONSTITUTION: This photographic element comprises a support for holding at least one kind of photographic silver halide emulsion incorporating at least one kind of a coupler high in pigment yield and releasing a pigment or a pigment precursor having an electrically neutral pigment chromophore, and this emulsion has low developability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a photographic element containing a photographic silver halide emulsion layer exhibiting low developability in combination with a high dye yield coupler.

[0002]

The present invention relates to the use of image dye-forming couplers that release dyes or dye precursors as coupling-off groups. These are so-called "High Dye-Yield (HDY)" couplers because two molecules of dye are formed when one molecule of coupler is consumed. Useful high dye yield couplers are described in Mooberry and Singer, US Pat. No. 4,840,884.
Specification (hereinafter, referred to as the 884 patent). These couplers release a second dye precursor having a neutral dye chromophore as it reacts with the oxidant of the color developer to form some dye. According to this 884 patent,
The novel couplers described can reduce silver halide concentration in photographic elements without degrading image quality.

Among the features desired in photographic elements are high speed (good low light sensitivity) and low fog (less non-imagewise development). The silver halide emulsions are prepared in such a way that high photographic speed and low fog development are most advantageously combined. This means, for example, by designing the iodide content and distribution, the grain size and morphology, the type of additives and sensitizations that reduce fog formation,
It is done depending on the degree of finishing such as changing the amount. As described above, there are various methods for controlling the fog, but each has an influence on the speed. Where speed / fog location is most advantageous, emulsions can be used most efficiently for imaging. However, at this speed / fog position, the emulsion
It may not give sufficient developed silver, so that when the imaging coupler is coated it will not have sufficient dye (Dmax
And density gradation) are not formed, and the film may not be useful as an actual film.

The development time (tod) in color negative processing by the Kodak Flexicolor C-41 ™ process is 3.25 minutes. If you change this tod to 2.5, 3.25, 4.25 minutes,
Both speed and fog increase for elements that have undergone constant step wedge exposure. When the emulsion was coated with an imaging coupler so that it was fully developed at each tod to reach maximum dye density (Dmax), as tod increased, Dmin increased rapidly enough to suppress film contrast. Alternatively, unless increased, the contrast increases with fog (read as Dmin).

The areas where the contrast and Dmin do not vary substantially with changes in development time (around 3.25 minutes employed in conventional photographic elements) are the most efficient for that coupler / silver combination. Area. Standard 3.
If the contrast and Dmin at 25 tod are lower than when they are in the maximum efficiency region, the emulsion is said to have poor developability or low density-forming ability.

High speed iodide-rich high speed emulsions have additives added at the time of finishing in a manner well known in the art to sensitize the grains to obtain the desired high speed and contrast. Added. This often results in relatively high Dmin values. D
Emulsions finished with lower min values typically have lower contrast but may exhibit sufficient speed. High speed, high iodide emulsions generally have low developability.

Emulsions with a high iodide content show a low contrast, so if this defect leads to inefficiencies in dye formation and dye covering power, a low iodide content is used to obtain the desired contrast. It is often necessary to coat at higher concentrations than the emulsion. It goes without saying that this interferes with the properties of the photographic element.

[0008]

The problem to be solved is an emulsion combined with a special coupler, and D
It is an object of the present invention to provide such emulsions which, when finished to a low min and contrast, exhibit improved sensitometric response over the more developable emulsions combined with conventional couplers.

[0009]

SUMMARY OF THE INVENTION The present invention is combined with at least one high dye yield coupler which releases a dye (or dye precursor) having an electrically neutral dye chromophore and is low. A photographic element is provided which comprises a support bearing at least one photographic silver halide emulsion exhibiting developability. The invention also includes a method of forming an image in an element according to the invention.

The photographic elements of this invention are finished to exhibit low Dmin and low developability, but give improved sensitometric response over the high developable emulsions in combination with conventional couplers. Such an emulsion is provided in combination with a coupler.

The present invention is directed to a photographic element comprising a support bearing a light-sensitive photographic silver halide emulsion layer which is combined with a coupler capable of forming a first dye by combining with an oxidized developer. As provided, the coupler also contains a coupling-off group that is released during development to form a second dye precursor, which precursor is -OC (O)-, -OC (S)-, -SC
(O) -, - SC ( S) - and -OC (= NSO ₂ R)
-Wherein R is alkyl or aryl which may or may not be substituted, and which has an electrically neutral dye chromophore bonded to a bonding group selected from the group consisting of: The amount of the coupler combined with the emulsion layer and the amount of silver in the layer have such a relationship that the molar ratio of the dye that can be produced from the coupler to the amount of silver contained in the layer is less than 1.0. Yes, and the amount of each coupler is 1g
/ M ^{2 or} less. The second dye preferably has a logarithmic calculated value of the neutral partition coefficient (ClogP) in the range of 3.5 to 5.5, but it is not essential.

The dye-forming coupler of the present invention is represented by the following general formula. COUP- (T) _m -L-DYE In the above formula, COUP is a base group of a coupler capable of reacting with an oxidized color developer at a coupling site to form a first dye, and T is m is an optional component of one or more timing groups from 0 to 2, L is a specific linking group, and DYE is a second dye. COUP is
It is a base part of a coupler capable of forming a dye by coupling with an oxidized form of a developer. As will be described in more detail hereinafter, the dye may be of any desired color and may be colorless or of the so-called universal type that is washed out of the photographic element during processing if desired. May be.

The photographic elements include US Pat. No. 2,367,
531, 2,423,730, 2,47
No. 4,293, No. 2,772,162, No. 2,8
95,826, 3,002,836, 3,
034,892, 3,041,236, 4,333,999 and 4,883,746 and Agfa Mitteilungen's publication "Farbkuppler-".
eine Literature Ubersicht '' (Band III, 156-17)
Image dye-forming couplers can also be included, such as those couplers that form cyan dyes upon reaction with oxidized color developing agents, as described in representative patent specifications and publications such as page 5, 1961). Such a coupler is preferably phenol or naphthol which produces a cyan dye when reacted with an oxidized color developing agent.

For couplers which form magenta dyes upon reaction with oxidized color developing agents, see US Pat.
No. 1,082, No. 2,343,703, No. 2,3
69,489, 2,600,788, 2,
908,573, 3,062,653, 3,152,896 and 3,519,429, and the publication "Farbkuppler-" by Agfa Mitteilungen.
eine Literature Ubersicht '' (Band III, Nos. 126-15)
6 pages, 1961) and representative patent specifications and publications. Such couplers are preferably pyrazolones, pyrazolotriazoles or pyrazolobenzimidazoles which form magenta dyes when reacted with oxidized color developers.

A coupler capable of forming a yellow dye upon reaction with an oxidized color developing agent is described in US Pat. No. 2,29,29.
No. 8,443, No. 2,407,210, No. 2,8
75,057, 3,048,194, 3,
265,506, 3,447,928, 4,022,620 and 4,443,536, and the publication "Farbkuppler-" by Agfa Mitteilungen.
eine Literature Ubersicht '' (Band III, 112--12)
6 pages, 1961) and representative patent specifications and publications. Such couplers are typically open chain ketomethylene based compounds.

For couplers which produce colorless products on reaction with oxidized color developing agents, see British Patent 861,1.
38, US Pat. Nos. 3,632,345 and 3,9.
No. 28,041, No. 3,958,993 and No. 3,961,959. Typically, such couplers are cyclic carbonyl-containing compounds that produce colorless products upon reaction with oxidized color developing agent.

For couplers which form black dyes on reaction with oxidized color developing agents, see US Pat.
9,231, 2,181,944, 2,3
33, 106 and 4,126,461 and representative patent specifications such as German Patent Application Publication Nos. 2,644,194 and 2,650,764. . Typically such couplers are resorcinols or m-aminophenols which produce black or neutral products on reaction with oxidized color developing agent.

Besides the above, so-called "universal" or "washout" couplers may be used.
These couplers do not contribute to image dye formation. Thus, for example, it is possible to use naphthols having unsubstituted carbamoyl or carbamoyl whose 2- or 3-position is substituted with a low molecular weight substituent. For this type of coupler, see, for example, US Pat.
No. 6,628, No. 5,151,343 and No. 5,
No. 234,800.

T may be absent, or one or two timing groups, as can be seen from the values of m between 0 and 2. Such groups are well known in the art, and include, for example, groups utilizing the cleavage reaction of hemiacetal (US Pat. No. 4,146,396, Japanese Patent Application Nos. 60-249148 and 60-60). 249
149), groups utilizing an electron transfer reaction in a conjugated system (US Pat. Nos. 4,409,323 and 4,42).
No. 1,845, Japanese Patent Application Nos. 57-188035 and 58.
-98728, 58-209736 and 58-
209738), groups utilizing cleavage of imino ketals (US Pat. No. 4,546,073),
A group which acts as a coupler or a reducing agent after a coupler reaction (US Pat. Nos. 4,438,193 and 4,61).
No. 8,571) and groups utilizing intramolecular nucleophilic substitution reactions (US Pat. No. 4,248,962). The timing group optionally attached to the L-DYE group of the present invention may be any group capable of releasing this L-DYE group. The above groups are not suitable as groups that release an L-DYE group, but can serve as the first of a series of two timing groups. Other timing groups are generally −
Suitable for releasing L-DYE groups. Most preferred are the timing groups described above. Generally, these are C
Containing a bond from an OUP or another timing group to an oxygen atom, which oxygen atom of the optionally substituted hydrocarbyl ring or heterocyclic ring is 1
One or two alkyl groups, which are optionally substituted with ring-bonded methyl groups, are attached at positions that can be conjugated, and the methyl groups are attached to the L-DYE group or the second timing group. Typical of such groups based on aromatic hydrocarbyl groups are shown below.

[0020]

[Chemical 1]

Wherein Z is selected from the group consisting of nitro, cyano, alkylsulfonyl, sulfamoyl (--SO ₂ NR ₂ ) and sulfonamide (--NRSO ₂ R) groups, where R is hydrogen or alkyl. Is a substituent,
R ^I , R ¹¹ and R ¹² are each independently hydrogen or a substituent that does not adversely affect the coupling reaction or the release reaction or the characteristics of the dye produced thereby. An example of such a group containing an aromatic heterocycle is given below.

[0022]

[Chemical 2]

In the above formula, R ^{9 to} R ¹² are each independently hydrogen or a substituent which does not adversely affect the coupling reaction or the release reaction or the characteristics of the dye produced thereby. L
Is COUP (or T if present) in the second dye
Is a group for bonding. L is − when the coupler is oxidatively coupled with the color developing agent during development processing.
It has a formula capable of cleaving L-DYE or-(T) _m- L-DYE. After COUP binds to the oxidized developer to form the first dye, -L-DYE or-
A fragment of (T) _m -L-DYE is released from COUP. Suitable groups for L are -OC (O)-, -OC
(S)-, -SC (O)-, -SC (S)-or -OC
(= NSO ₂ R)-, where R is alkyl or aryl, which may be substituted or unsubstituted. Such groups allow the above fragment to be cleaved from COUP and also cleaved from DYE. U.S. Pat. No. 4,840,884 generally describes photographic elements using high dye yield couplers having electrically neutral chromophores, the contents of which are incorporated herein by reference. It will be adopted by the matter. In addition, a particularly suitable coupler containing a methine dye chromophore is disclosed in the inventor's co-pending application entitled "Phot
ographic Element Containing A High Dye-Yield Coupl
er With A Methine Dye Chromophore ”.

In one embodiment of the present invention, with proper selection of ClogP, it is possible to transfer --L-DYE or-(T) _m --L-DYE while the linking group is attached to the second dye. However, when the linking group is cleaved from the second dye, D
It is considered that YE cannot diffuse. This is achieved provided that the calculated neutral partition coefficient (ClogP) of the second dye is in the range 3.5-5.5.
Thus, when the linking group is cleaved from the second dye, it no longer contains the charged, highly polar portion exhibited by the linking group. Then, after the bonding group is separated, the second dye does not freely diffuse, so that the stability of the image dye becomes good from the viewpoint of long-term image stability.

The neutral partition coefficient is the distribution ratio of compounds in equilibrium between octanol and water. The calculations were obtained using Medchem software, version 3.54, Medical Chemistry Project at Pomona University, Claremont, Calif. For a recent description of this method, see Albert J. Leo, Comprehensive Medi.
cinal Chemistry "(C. Hansch, PG Sammes and JBT
Aylor, Pergamon Press, New York, Volume 4, 1990
Year).

The couplers of this invention release a second dye having an electrically neutral chromophore. This means that the chromophore in its characteristic hue has no superficial charge. The second dye of the present invention preferably contains a substituted nitrogen atom bonded to a bonding group. Such dyes are described, for example, in US Pat.
It can be of any of the types described in 840,884 and can be synthesized as described herein.

The DYE described includes any releasable, electrically neutral dye which can stabilize the hue of the dye without mordanting the dye formed. The release mechanism can be initiated by the oxidized reducing agent.
In US Pat. No. 4,840,884, the term "D
“YE” is defined so that adjacent nitrogen atoms are not part of DYE, but the definition herein includes these nitrogen atoms. In each case, the composition of the dye produced by the release is the same.

The R ¹ substituent of --NR ¹ --may be any substituent as long as it does not adversely affect the coupler. When —NR ¹ — is part of an auxochrome, R ¹ is, for example, hydrogen or alkyl, for example C 1-42.
Alkyl (including methyl, ethyl, propyl, n-butyl, t-butyl or eicosyl) or aryl such as phenyl. When the nitrogen atom attached to L is part of a chromophore, R ¹ becomes an integral part of that chromophore. Preferred R ¹ groups when R ¹ is part of the dye auxochrome alkyl, for example, 1 to 18 alkyl carbon atoms. R ¹ when it is part of a chromophore is, for example, substituted or unsubstituted aryl, such as phenyl.

The type and size of the DYE substituents can be selected to provide a DYE distribution coefficient that allows the desired degree of diffusion. A particularly useful type of DYE moiety is described below. Azo dye moiety containing -NR ¹ -group represented by the following structural formula

[0030]

[Chemical 3]

In the above formula, R ²⁵ is hydrogen or a substituent such as alkyl, and R ²⁶ and R ²⁷ each independently represent hydrogen or one or more substituents such as alkyl. Azamethine dye moiety containing -NR ¹ -group represented by the following structural formula

[0032]

[Chemical 4]

Wherein R ²⁸ is hydrogen or one or more substituents such as alkyl, R ²⁹ is hydrogen or a substituent such as alkyl, and EWG is an electron withdrawing group. Methine dye moiety containing -NR ¹ -group represented by the following structural formula

[0034]

[Chemical 5]

Wherein R ³⁰ and R ³¹ are each independently a substituent such as hydrogen or alkyl, R ^30a is hydrogen or one or more substituents such as alkyl, and EW
G is an electron-withdrawing group having a positive Hammett sigma (para) value.

The term "DYE" also includes dye precursors in which the stated substituted nitrogen atom is an integral part of the chromophore.
This is also referred to herein as the leuco dye moiety.
Such dye precursors include, for example:

[0037]

[Chemical 6]

In the above formula, R ³² is cleaved during processing by NH
Or a group leaving N = N, and R ³³ is aryl, for example substituted phenyl.

[0039]

[Chemical 7]

In the above formula, R ³⁴ is cleaved during processing to NH
Or a group leaving N = C, and EWG is an electron-withdrawing group as defined above. Examples of cyan dyes, magenta dyes, yellow dyes and leuco dyes are given below. A. Cyan dye

[0041]

[Chemical 8]

In the above formula, R ³⁵ is a substituent that does not adversely affect the dye, for example, alkyl, and R ³⁶ is a substituent, for example, an electron-emitting group having a Hammett sigma (para) value lower than 0. , And R ³⁷ is one or more kinds of substituents, for example, a highly electron-withdrawing group having a Hammett sigma (para) value of 0.23 or more. B. Magenta dye

[0043]

[Chemical 9]

Wherein R ³⁸ is a substituent that does not adversely affect the dye, eg alkyl, R ³⁹ is a substituent, eg an electron emissive group as defined above, and R
⁴⁰ is a substituent, for example, a group having a strong electron-withdrawing property as defined above. C. Yellow dye

[0045]

[Chemical 10]

In the above formula, R ⁴¹ is alkyl, R ⁴² is alkoxy, alkyl or H, and R ⁴³ is alkyl or H.

[0047]

[Chemical 11]

Wherein R ⁴⁴ is alkyl, R ⁴⁵ is alkoxy, alkyl or H, R ⁴⁶ is alkyl or aryl, and X is --O-- or --NR ^* -(R
^* Is H, alkyl or aryl). D. Leuco dye

[0049]

[Chemical 12]

Wherein R ⁴⁷ and R ⁴⁸ are each independently hydrogen or alkyl, R ⁴⁹ is an electron emissive group as previously defined, and R ⁵¹ is as previously defined. It is a group with a strong electron-withdrawing property.

[0051]

[Chemical 13]

In the above formula, R⁵²And R⁵⁴Are each independently hydrogen
Or a substituent, R⁵³Is -NHR ^aOr-NHSO₂
R^a(R^aIs a substituent) and R⁵⁵And R⁵⁶
Are each independently hydrogen or a substituent. The dye of the present invention
Preferable examples of high yield couplers will be given.

[0053]

[Chemical 14]

[0054]

[Chemical 15]

[0055]

[Chemical 16]

[0056]

[Chemical 17]

[0057]

[Chemical 18]

[0058]

[Chemical 19]

[0059]

[Chemical 20]

[0060]

[Chemical 21]

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23]

[0063]

[Chemical formula 24]

[0064]

[Chemical 25]

[0065]

[Chemical formula 26]

[0066]

[Chemical 27]

[0067]

[Chemical 28]

[0068]

[Chemical 29]

[0069]

[Chemical 30]

[0070]

[Chemical 31]

[0071]

[Chemical 32]

[0072]

[Chemical 33]

[0073]

[Chemical 34]

[0074]

[Chemical 35]

[0075]

[Chemical 36]

[0076]

[Chemical 37]

[0077]

[Chemical 38]

[0078]

[Chemical Formula 39]

[0079]

[Chemical 40]

[0080]

[Chemical 41]

[0081]

[Chemical 42]

[0082]

[Chemical 43]

[0083]

[Chemical 44]

[0084]

[Chemical formula 45]

[0085]

[Chemical formula 46]

[0086]

[Chemical 47]

[0087]

[Chemical 48]

[0088]

[Chemical 49]

[0089]

[Chemical 50]

[0090]

[Chemical 51]

[0091]

[Chemical 52]

[0092]

[Chemical 53]

[0093]

[Chemical 54]

[0094]

[Chemical 55]

[0095]

[Chemical 56]

[0096]

[Chemical 57]

[0097]

[Chemical 58]

[0098]

[Chemical 59]

[0099]

[Chemical 60]

[0100]

[Chemical formula 61]

[0101]

[Chemical formula 62]

[0102]

[Chemical formula 63]

[0103]

[Chemical 64]

[0104]

[Chemical 65]

[0105]

[Chemical formula 66]

[0106]

[Chemical formula 67]

[0107]

[Chemical 68]

[0108]

[Chemical 69]

[0109]

[Chemical 70]

[0110]

[Chemical 71]

[0111]

[Chemical 72]

[0112]

[Chemical formula 73]

[0113]

[Chemical 74]

[0114]

[Chemical 75]

[0115]

[Chemical 76]

[0116]

[Chemical 77]

[0117]

[Chemical 78]

[0118]

[Chemical 79]

[0119]

[Chemical 80]

[0120]

[Chemical 81]

[0121]

[Chemical formula 82]

[0122]

[Chemical 83]

[0123]

[Chemical 84]

[0124]

[Chemical 85]

[0125]

[Chemical 86]

[0126]

[Chemical 87]

[0127]

[Chemical 88]

[0128]

[Chemical 89]

[0129]

[Chemical 90]

[0130]

[Chemical Formula 91]

[0131]

[Chemical Formula 92]

[0132]

[Chemical formula 93]

[0133]

[Chemical 94]

[0134]

[Chemical 95]

[0135]

[Chemical 96]

[0136]

[Chemical 97]

[0137]

[Chemical 98]

[0138]

[Chemical 99]

[0139]

[Chemical 100]

[0140]

[Chemical 101]

[0141]

[Chemical 102]

[0142]

[Chemical 103]

[0143]

[Chemical 104]

[0144]

[Chemical 105]

[0145]

[Chemical formula 106]

[0146]

[Chemical formula 107]

[0147]

[Chemical 108]

[0148]

[Chemical 109]

[0149]

[Chemical 110]

[0150]

[Chemical 111]

[0151]

[Chemical 112]

[0152]

[Chemical 113]

[0153]

[Chemical 114]

[0154]

[Chemical 115]

[0155]

[Chemical formula 116]

In addition to the above, photographic elements of this invention generally contain low coverage silver and the molar ratio of dyes theoretically formable from the couplers of this invention to the silver present in the layer. You can hope that is low. More specifically, the amount of silver contained in the elements of this invention is less than 90% of the amount typically used in elements using conventional couplers and exhibiting comparable sensitometry. It is not possible to specify the exact amount of silver that can be used. This amount depends on the reactivity of the coupler and many other components of the element. However, when the couplers of the present invention are used, the amount of silver required by conventional couplers in order to achieve a certain target sensitometry is significantly increased,
That is, it can be reduced by 10% to 35%, or nearly 50%.

According to the present invention, the coating amount of silver is reduced, and the molar ratio of the dye theoretically formable from the coupler of the present invention having a high dye yield to silver is reduced. This not only preserves the silver and dye necessary to achieve the desired sensitometry, but also the mass efficiency in the coupler needed to produce the required color image density and contrast. Also provide.

It is possible to provide a coupler according to the invention such that the first dye is ballasted so that it does not migrate completely, or that it has a limited mobility in developers and other processing solutions. it can. It is also a conventional image coupler or PU in combination with a silver halide emulsion of the invention, as described in more detail herein.
It is also encompassed by the present invention to include one or more new couplers that are G-releasing couplers.

The dyes produced by the couplers of this invention can be in any desired color gamut. In today's color negatives, yellow, cyan and magenta are the most commonly used areas. The first and second dyes of the present invention are in the same range, i.e. 400-500n.
If it has an absorption maximum at m, 500 to 600 nm or 600 to 700 nm, it has the same color. If the two dyes are the same color, their absorption maxima are typically within 25 nm of each other. Photographic elements in which the present invention can be utilized include, for example, image capture color negatives, color prints and reversals.

In a particularly preferred embodiment of the present invention the silver halide layer of the present invention represents at least one layer, preferably a fast layer, of a multilayer color record. Usually such layers overlie the slower layers of the color record and also contain larger size silver halide grains for speed purposes. When the present invention is applied to this layer, the graininess is remarkably improved, and at the same time, since the layer can be thinned, deterioration of the optical image formed in the lower layer can be reduced. The present invention is particularly suited to tabular grains which allow excellent grain reduction. It may also be desirable to use the couplers of this invention in less sensitive imaging layers where finer grain emulsions are typically used.

In part, the desired results are possible by reducing the coating weight of imaging coupler and formable image dye relative to the coating weight of silver in the layer. Thus, the molar ratio of formable dye to silver halide (theoretical amount of first and second dye) is less than 1.0. More preferably, this ratio is less than 0.8, and 0.55
Often, good results are obtained.

The emulsion of the present invention exhibits a lower developability than those conventionally used. For example, the developability of an emulsion can be varied by changing the content of the particular halide used in the emulsion. The developability is
For example, increasing the iodide content, modifying the iodide distribution, changing the grain size, changing the grain morphology, and even reducing fog formation during emulsion preparation. It can be lowered depending on the degree of sensitization and the degree of finishing by changing the kind or amount of additives.

In the present invention, any of the generally known emulsions including three-dimensional cubic grain emulsions and tabular grain emulsions are useful. These are referred to in the publication "Research Discl" cited herein.
All of them are described in "Osure". These emulsions may be polydisperse or monodisperse. In particular, an emulsion containing iodide in an amount of 3 mol% or more, typically 6 mol% or more is suitable.

In more detail, a standard emulsion capable of complete development within the standard development time of 3.25 minutes and having the same size, speed and morphology (both conventional image coupler C-1 The emulsion in question has (a) a lower Dmin and a standard emulsion than the standard emulsion for the same development time when compared to the standard emulsion containing conventional image coupler.
(b) The emulsion has "low developability" when it shows a contrast of 90% or less.

Regarding further development of HDY couplers that can be used in combination with the present invention, US patent application Ser. Nos. 08 / 250,258 and 08/2, filed on the same date as the present application.
50,744, 08 / 250,416 and 08 / 250,199, which are incorporated herein by reference in their entirety.

The method of this invention comprises the step of exposing a photographic element of this invention and then contacting the element with a color developing agent to form a color image. Color developers are described in more detail later in this specification.

The term “substituent” as used herein
Unless otherwise specified, the definition range is wide. Substituents are, for example, halogen (eg chlorine, bromine or fluorine), nitro, hydroxyl, cyano and -CO.
₂ H; and a group which may be further substituted, for example,
Alkyl including straight chain or branched chain alkyl [eg,
Methyl, trifluoromethyl, ethyl, t-butyl, 3
-(2,4-di-t-amylphenoxy) propyl and tetradecyl], alkenyl (eg, ethylene, 2-butene), alkoxy [eg, methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, Hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy and 2-dodecyloxyethoxy],
Aryl (eg, phenyl, 4-t-butylphenyl,
2,4,6-trimethylphenyl, naphthyl), aryloxy (eg, phenoxy, 2-methylphenoxy, α
-Or β-naphthyloxy and 4-tolyloxy), carbonamide [eg, acetamide, benzamide, butyramide, tetradecanamide, α- (2,4-di-t
-Pentylphenoxy) acetamide, α- (2,4-
Di-t-pentylphenoxy) butyramide, α- (3
-Pentadecylphenoxy) hexanamide, α- (4
-Hydroxy-3-t-butylphenoxy) tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamide, N-succinimide, N-phthalimide , 2,5-dioxo-1-oxazolidinyl,
3-dodecyl-2,5-dioxo-1-imidazolyl,
N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5- ( The-t-
Pentylphenyl) carbonylamino, p-dodecylphenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N, N-dimethylureido,
N-methyl-N-dodecyl ureido, N-hexadecyl ureido, N, N-dioctadecyl ureido, N, N-
Dioctyl-N'-ethylureido, N-phenylureido, N, N-diphenylureido, N-phenyl-N
-P-toluylureido, N- (m-hexadecylphenyl) ureido, N, N- (2,5-di-t-pentylphenyl) -N'-ethylureido and t-butylcarbonamide], sulfonamide ( Examples, methylsulfonamide, benzenesulfonamide, p-toluylsulfonamide, p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide, N, N-dipropyl-sulfamoylamino and hexadecylsulfonamide), sulfamoyl { Examples, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N,
N-dimethylsulfamoyl, N- [3- (dodecyloxy) propyl] sulfamoyl, N- [4- (2,4
-Di-t-pentylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl and N-dodecylsulfamoyl}, carbamoyl {eg, N
-Methylcarbamoyl, N, N-dibutylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,2
4-di-t-pentylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl and N, N-dioctylcarbamoyl}, acyl [eg, acetyl, (2,4-di-t-amylphenoxy) acetyl , Phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl, methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl and dodecyloxycarbonyl], sulfonyl (eg, methoxysulfonyl, octyloxy) Sulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,
4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl and p-toluylsulfonyl), sulfonyloxy (eg, dodecylsulfonyl). Oxy and hexadecylsulfonyloxy), sulfinyl (eg, methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl and p-toluylsulfinyl), thio [eg,
Ethylthio, octylthio, benzylthio, tetradecylthio, 2- (2,4-di-t-pentylphenoxy)
Ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio and p-tolylthio], acyloxy (eg, acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N -Ethylcarbamoyloxy and cyclohexylcarbonyloxy), amines (eg phenylanilino, 2-chloroanilino, diethylamine, dodecylamine), imino [eg 1- (N-phenylimido) ethyl, N-succinimide or 3-benzylhydan. Toynyl], phosphate (eg, dimethyl phosphate and ethyl butyl phosphate), phosphite (eg, diethyl phosphite and dihexyl phosphite), oxygen, nitrogen and a minor amount selected from the group consisting of sulfur. Each containing a 3- to 7-membered heterocycle containing one kind of hetero atom and a carbon atom, and each of which may be substituted, a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group (eg, 2 -Furyl, 2-thienyl, 2
-Benzimidazolyloxy or 2-benzothiazolyl), quaternary ammonium (eg triethylammonium) as well as silyloxy (eg trimethylsilyloxy).

The particular substituents used can be chosen to obtain the photographic properties desired for a particular application and can include, for example, hydrophobic groups, solubilizing groups, and the like. Generally, the above groups and their substituents can include those having from 1 to 42 (usually less than 24) carbon atoms, although the number of carbon atoms can be further increased depending on the particular substituent selected. In some cases. Moreover, as mentioned above, the substituents themselves may optionally be substituted with any of the above groups.

The materials of the present invention can be used in any manner known in the art and in any combination. The materials of this invention are typically mixed with a silver halide emulsion and the mixture is coated as a layer on a support to form part of a photographic element. Alternatively, they can be incorporated adjacent to the silver halide emulsion layer which is reactively associated with development products such as oxidized color developer during development. Thus, as used herein, the term "combined" is in the immediate vicinity where the compound is in the silver halide emulsion layer or where the compound may react with silver halide development products during processing. Means that.

In order to control the migration of various components, it may be desirable to include high molecular weight hydrophobic species or "ballast" groups in the component molecules. A typical ballast base is
Included are substituted or unsubstituted alkyl or aryl groups containing 8 to 42 carbon atoms. Representative substituents attached to such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl,
Included are acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamide and sulfamoyl groups, these substituents typically containing 1-42 carbon atoms. Moreover, such a substituent may be further substituted.

The photographic elements can be single color elements or multicolor elements. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can contain a single emulsion layer or multiple emulsion layers sensitive to a particular spectral region. The layers of the photographic element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another format, the emulsions sensitive to each of the three primary regions of the spectrum can be arranged as a single segmented layer.

A typical multicolor photographic element is a cyan dye image-forming unit containing one or more red-sensitive silver halide emulsion layers in combination with at least one cyan dye-forming coupler and at least one magenta. A magenta dye image-forming unit containing one or more green-sensitive silver halide emulsion layers in combination with a dye-forming coupler;
1 combined with a variety of yellow dye-forming couplers
And a yellow dye image-forming unit containing one or more blue-sensitive silver halide emulsion layers. The element may further contain additional layers such as filter layers, interlayers, overcoat layers, subbing layers, and the like.

If desired, a magnetic layer can be applied to the photographic element and used. For the application of the magnetic layer,
Research Disclosure (November 1992, Item 34390, Kenneth, UK)
Mason Publications (Dudley An
nex, 12a North Street, Emsworth, Hampshire, P0107D
Q)), and US Pat. No. 5,252,441.
No. 5,254,449 and 5,25
No. 4,446, which is incorporated herein by reference.

Color negative films using such layers can be used in combination with cameras that can record and store various useful information relating to film use and history. it can. As a special example, there is exposure information for each scene or roll.
These films can then be searched for exposure information and usage information for the film as well as film property information, and processing can be modified as necessary to ensure optimal performance and, if desired, And record details regarding the processing of the magnetic layer. These films can then be searched for both film and process history information and, if necessary, based on that information, printing time, printing light intensity, printing light color balance, printing light color temperature. , Printing magnification or printing lens adjustment, exposure, or printing time, and printing using such an automated printer that can change the exposure characteristics selected from the color filters, from various coloring materials A well-balanced display print can be produced. These layers, even if located on the same side of the support as the photosensitive layer,
Alternatively, the support may be arranged so as to be located between the magnetic layer and the photosensitive layer. This information is useful in modifying film processing and printing conditions to help produce pleasing images.

It is particularly conceivable to use a support bearing a magnetic layer as described above.

In the following description of the materials suitable for use in the emulsions and elements of this invention, the Research Disclosure (1) available as above is set forth.
December 1989, Item 308119). In the present specification, this document is referred to as "Resea" hereinafter.
rch Disclosure ”.
The contents of this Research Disclosure, including the patent specifications and publications cited therein, are incorporated herein by reference. Also, the section referred to below means this Rese
Refers to the section of Arch Disclosure. In addition, the material of the present invention can be obtained from the Japan Patent Office, JP-A-94-6023 (Invention Society,
It is also possible to use in combination with the materials described in (March 1994). In this specification, this publication is incorporated by reference.

The silver halide emulsions used in the elements of this invention can be negative or positive working. Appropriate emulsions and their manufacturing methods, as well as chemical and spectral sensitization methods
It is described in Sections I-IV. See Sections VII-XXI for colorants and development modifiers.
It is described in. Section IX for vehicles
It is described in. Various additives such as optical brighteners, antifoggants, stabilizers, light-absorbing substances and light-scattering substances, hardeners, coating aids, plasticizers, lubricants and matting agents are described in, for example, Sections V, VI, VIII, X, XI, XII and X
VI. Section X for manufacturing methods
IV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVIII, respectively.

Coupling-off groups are well known in the art. Such groups can determine the chemical equivalent number of the coupler, that is, whether it is a 2-equivalent coupler or a 4-equivalent coupler, and can control the reactivity of the coupler. Such a group, after being released from the coupler, exerts functions such as dye formation, hue adjustment, development acceleration or development inhibition, bleach acceleration or bleach inhibition, electron transfer acceleration, color correction, etc.,
It can have a beneficial effect on the layer in which the coupler is coated or on other layers in the photographic recording material.

The presence of hydrogen at the coupling site gives a 4-equivalent coupler, and the presence of another coupling-off group usually gives a 2-equivalent coupler. Representative types of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, heterooxy, sulfonyloxy, acyloxy, acyl, heterocycle, sulfonamide, mercaptotetrazole, benzothiazole, mercaptopropionic acid, phosphonyl. Included are oxy, arylthio and arylazo. These coupling-off groups are described, for example, in US Pat. No. 2,455,169.
No., No. 3,227,551, No. 3,432,52
No. 1, No. 3,476,563, No. 3,617,2
No. 91, No. 3,880,661, No. 4,052.
212 and 4,134,766 and British Patents 1,466,728 and 1,531,92.
7 and 1,533,039 and British Patent Application Publication Nos. 2,006,755A and 2,017,7.
No. 04A, which is incorporated herein by reference.

Known ballast or coupling-off groups, such as those described in US Pat. Nos. 4,301,235, 4,853,319 and 4,351,897. It may be useful to use a combination of couplers, any of which may contain The coupler can contain solubilizing groups as described in US Pat. No. 4,482,629. Also, the coupler may be used in combination with "wrong" colored couplers (eg, to adjust interlayer correction levels), and in color negative applications, EP 213,490. JP-A-58-
172,647, US Pat. No. 2,983,608
No. 4,070,191 and 4,273,8
No. 61, German Patent Application Publication No. 2,706,117
No. 2,643,965, British Patent No. 1,
530,272 and JP-A-58-11393.
A masking coupler as described in Japanese Patent No. 5 can also be used in combination. The masking coupler may be shifted or blocked, as desired. For example, in a color negative element, the material of the element, including the support bearing the following layers from top to bottom, can be replaced or supplemented with the material of the invention.

(1) One or more overcoat layers containing an ultraviolet absorber; (2) "Coupler 1": benzoic acid, 4-chloro-3-
((2- (4-Ethoxy-2,5-dioxo-3- (phenylmethyl) -1-imidazolidinyl) -3- (4-
Methoxyphenyl) -1,3-dioxopropyl) amino)-, a high-sensitivity yellow layer containing dodecyl ester, and the same compound as "coupler 2": propanoic acid,
2-[[5-[[4- [2-[[[2,4-bis (1,
1-dimethylpropyl) phenoxy] acetyl] amino] -5-[(2,2,3,3,4,4,4-heptafluoro-1-oxobutyl) amino] -4-hydroxyphenoxy] -2,3- Dihydroxy-6-[(propylamino) carbonyl] phenyl] thio] -1,3,4
-Thiadiazol-2-yl] thio]-, methyl ester, and "coupler 3": 1-((dodecyloxy) carbonyl) ethyl (3-chloro-4-((3- (2-chloro-4-(( 1-tridecanoylethoxy) carbonyl) anilino) -3-oxo-2-((4) (5)
(6)-(phenoxycarbonyl) -1H-benzotriazol-1-yl) propanoyl) amino)) slow yellow layer containing together with benzoate, a two-layer yellow pack;

(3) Intermediate layer containing fine metallic silver; (4) "Coupler 4": benzamide, 3-((2-
(2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4,5-dihydro-5-oxo-1- (2,4,6-trichlorophenyl)- 1H-pyrazol-3-yl)-, "Coupler 5": benzamide, 3-((2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- ( 4 ', 5'-dihydro-
5'-oxo-1 '-(2,4,6-trichlorophenyl) (1,4'-bi-1H-pyrazol) -3'-yl)
-, "Coupler 6": carbamic acid, (6-(((3-
(Dodecyloxy) propyl) amino) carbonyl)-
5-hydroxy-1-naphthalenyl)-, 2-methylpropyl ester, "coupler 7": acetic acid, ((2-
((3-(((3- (Dodecyloxy) propyl) amino) carbonyl) -4-hydroxy-8-(((2-methylpropoxy) carbonyl) amino) -1-naphthalenyl) oxy) ethyl) thio)- , And “coupler 8”: benzamide, 3-((2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4,5-dihydro-4-).
((4-Methoxyphenyl) azo) -5-oxo-1-
Highly sensitive magenta layer containing (2,4,6-trichlorophenyl) -1H-pyrazol-3-yl)-, and "coupler 9": 2-propenoic acid, butyl ester, styrene and N- [1- ( 2,4,6-Trichlorophenyl)-
4,5-Dihydro-5-oxo-1H-pyrazolo-3-
Il] -2-methyl-2-propenamide in a weight ratio of 1:
Three-component copolymer containing 1: 2, and "Coupler 1
0 ": tetradecanamide, N- (4-chloro-3-
((4-((4-((2,2-dimethyl-1-oxopropyl) amino) phenyl) azo) -4,5-dihydro-5-oxo-1- (2,4,6-trichlorophenyl) -1H-pyrazol-3-yl) amino) phenyl)
A three-layer magenta pack containing an intermediate magenta layer and a low-sensitivity magenta layer each containing -in addition to coupler 3 and coupler 8;

(5) Intermediate layer; (6) High-sensitivity cyan layer containing coupler 6 and coupler 7, coupler 6 and "coupler 11": 2,7-naphthalenedisulfonic acid, 5- (acetylamino) -3. −
((4- (2-((3-(((3- (2,4-bis (1,1-dimethylpropyl) phenoxy) propyl
An intermediate cyan layer containing amino) carbonyl) -4-hydroxy-1-naphthalenyl) oxy) ethoxy) phenyl) azo) -4-hydroxy-, a disodium salt, and a slow cyan containing coupler 2 and coupler 6. A three-layer cyan pack containing a layer; (7) an undercoat layer containing the coupler 8; and (8) an antihalation layer.

In the color paper format, the material of the element, including the support carrying the following layers from top to bottom, can be replaced or supplemented with the material of the invention.

(1) One or more overcoats; (2) "Coupler 1": butanamide, 2- (2,4-
Bis (1,1-dimethylpropyl) phenoxy) -N-
(3,5-dichloro-2-hydroxy-4-methylphenyl)-, "coupler 2": acetamide, 2- (2,
4-bis (1,1-dimethylpropyl) phenoxy)-
N- (3,5-dichloro-2-hydroxy-4-, as well as UV stabilizers: phenol, 2- (5-chloro-2H-
Benzotriazol-2-yl) -4,6-bis (1,
1-dimethylethyl)-; phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1-dimethylethyl)-; phenol, 2- (2H-benzotriazol-2-yl) -4 -(1,1-dimethylethyl)
-6- (1-methylpropyl)-; and phenol, 2
-(2H-benzotriazol-2-yl) -4,6-
Bis (1,1-dimethylpropyl)-, as well as poly (t
-Butylacrylamide) dye stabilizer, (3) intermediate layer, (4) "coupler 3": octanamide, 2- [2,4]
-Bis (1,1-dimethylpropyl) phenoxy] -N
-[2- (7-Chloro-6-methyl-1H-pyrazolo [1,5-b] [1,2,4] triazol-2-yl)
Propyl]-, and 1,1'-spirobi (1H-indene), 2,2 ', 3,3'-tetrahydro-3,3.
Magenta layer containing 3 ', 3'-tetramethyl-5,5', 6,6'-tetrapropoxy-; (5) intermediate layer; and (6) "coupler 4": 1-imidazolidineacetamide, N -(5-((2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -2-chlorophenyl) -α- (2,2-dimethyl-1-oxopropyl ) -4-Ethoxy-2,5-dioxo-3- (phenylmethyl) -containing yellow layer.

In the reversal format, the material of the element, including the support carrying the following layers from top to bottom, can be replaced or supplemented with the material of the invention.

(1) One or more overcoat layers; (2) Non-sensitized silver halide-containing layer; (3) "Coupler 1": benzoic acid, 4- (1-(((2
-Chloro-5-((dodecylsulfonyl) amino) phenyl) amino) carbonyl) -3,3-dimethyl-2-
High-sensitivity yellow layer containing oxobutoxy)-, 1-methylethyl ester; coupler 1 and "coupler 2":
Benzoic acid, 4-chloro-3-[[2- [4-ethoxy-
2,5-dioxo-3- (phenylmethyl) -1-imidazolidinyl] -4,4-dimethyl-1,3-dioxopentyl] amino]-, an intermediate yellow layer containing dodecyl ester; and coupler 2 A low-sensitivity yellow layer containing a three-layer yellow layer pack; (4) intermediate layer; (5) fine particle silver layer; (6) intermediate layer; (7) "coupler 3": N- [1- ( 2,5-Dichlorophenyl) -4,5-dihydro-5-oxo-1H-pyrazolo-3-yl] -2-methyl-2-propenamide containing 2-propenoic acid, butyl ester, polymer;
"Coupler 4": benzamide, 3-((2-2,4-
Bis (1,1-dimethylpropyl) phenoxy) -1-
Oxobutyl) amino) -N- (4,5-dihydro-5
-Oxo-1- (2,4,6-trichlorophenyl)-
1H-pyrazol-3-yl)-; and "coupler 5": benzamide, 3-(((2,4-bis (1,1
-Dimethylpropyl) phenoxy) acetyl) amino)
-N- (4,5-dihydro-5-oxo-1- (2,
4,6-Trichlorophenyl) -1H-pyrazol-3-
And a stabilizer, 1,1′-spirobi (1H-indene), 2,2 ′, 3,3′-tetrahydro-3,3,3 ′, 3′-tetramethyl-5, 5 ',
A three-layer magenta pack containing a fast magenta layer containing 6,6'-tetrapropoxy- and a slow magenta layer containing the same stabilizer and couplers 4 and 5;

(8) One or more intermediate layers which may contain finely grained non-sensitized silver halide; (9) "Coupler 6": tetradecanamide, 2- (2
-Cyanophenoxy) -N- (4-((2,2,3,
3,4,4,4-heptafluoro-1-oxobutyl)
Amino) -3-hydroxyphenyl) -containing high-sensitivity cyan layer; "Coupler 7": butanamide, N- (4
-((2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -2-
Hydroxyphenyl) -2,2,3,3,4,4,4-
Heptafluoro- and "Coupler 8": Hexanamide, 2- (2,4-bis (1,1-dimethylpropyl)
Phenoxy) -N- (4-((2,2,3,3,4
4,4-heptafluoro-1-oxobutyl) amino)
A three-layer cyan pack including an intermediate cyan layer containing -3-hydroxyphenyl); (10) one or more intermediate layers that may contain fine grained unsensitized silver halide; and (11) an antihalation layer.

The materials of the present invention can also be used in combination with materials that enhance or control processing steps such as bleaching and fixing to improve image quality. European Patent No. 1
93,389, 301,477, U.S. Pat. Nos. 4,163,669, 4,865,956 and 4,923,784, which release bleaching accelerators. Sometimes type couplers are useful. Further, nucleating agents, development accelerators or precursors thereof (British Patent No. 2,097,140; No. 2,131,188); electron transfer agents (US Pat. No. 4,859,578) ;
No. 4,912,025); antifoggants and color mixing inhibitors such as hydroquinone, aminophenols, amines, derivatives of gallic acid; catechols; ascorbic acid; hydrazides; sulfonamidephenols; and non-color couplers. The use of combined compositions is also contemplated.

The materials according to the invention can also be used as oil-in-water dispersions, latex dispersions or solid particle dispersions in combination with filter dye layers containing yellow, cyan and / or magenta filter dyes or colloidal silver sols. it can. In addition, they are "smearing"
Couplers (eg US Pat. No. 4,366,237, EP 96,570, US Pat. No. 4,420,556).
No. 4,543,323) and US Pat. No. 4,543,323). The composition can also be applied or blocked in a protected form as described in, for example, Japanese Patent Application No. 61-258,249 or US Pat. No. 5,019,492.

The materials of this invention can also be used with image-modifying compounds such as "Development Inhibitor Releasing" (DIR) compounds. DIR's useful in combination with the compositions of the present invention are known in the art and examples of which are described in the following patent documents: US Pat. No. 3,137,578, US Pat. 3,148,022,
No. 3,148,062, No. 3,227,554
No. 3,384,657, No. 3,379,52
No. 9, No. 3,615, 506, No. 3,617, 2
No. 91, No. 3,620, 746, No. 3,701,
No. 783, No. 3,733, 201, No. 4,04
No. 9,455, No. 4,095,984, No. 4,1
No. 26,459, No. 4,149,886, No. 4,
No. 150,228, No. 4,211,562, No. 4,248,962, No. 4,259,437, No. 4,362,878, No. 4,409,323,
No. 4,477,563, No. 4,782,012
No. 4,962,018, 4,500,63
No. 4, No. 4,579, 816, No. 4, 607, 0
No. 04, No. 4,618, 571, No. 4,678,
No. 739, No. 4,746,600, No. 4,74
No. 6,601, No. 4,791,049, No. 4,8
57,447, 4,865,959, and 4,
880,342, 4,886,736, 4,937,179, 4,946,767, 4,948,716, 4,952,485,
No. 4,956,269, No. 4,959,299
Nos. 4,996,835 and 4,985,3
No. 36; British Patent Nos. 1,560,240, 2,007,662, 2,032,914 and 2,099,167; German Patent No. 2, 84
No. 2,063, No. 2,937,127, No. 3,6
36,824 and 3,644,416;
And European Patents 272,573 and 335,31
No. 9, No. 336, 411, No. 346, 899,
No. 362,870, No. 365,252, No. 3
65,346, 373,382, 376.
No. 212, No. 377, 463, No. 378, 236
No. 384,670, No. 396,486, No. 401,612, and No. 401,613.

Such compounds are represented by Photograph
hic Science and Engineerine
C. g. (Vol. 13, p. 174, 1969).
R. Barr, J .; R. Thirdr and P.P. W. V
Ittum's development inhibitor release type (DI for color photography
R) couplers ”, which are incorporated herein by reference. Generally, development inhibitor releasing (DIR) couplers include a coupler moiety and an inhibitor coupling-off moiety (IN). Inhibitor release couplers are time-delayed (D) that further include a timing moiety or chemical switch that delays the release of the inhibitor.
IAR coupler). Examples of typical inhibitor moieties include oxazole, thiazole, diazole, triazole, oxadiazole, thiadiazole, oxathiazole, thiatriazole, benzotriazole, tetrazole, benzimidazole, indazole, isoindazole, mercaptotetrazole,
Selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzodiazole, mercaptooxazole, mercaptothiadiazole, mercaptothiazole, mercaptotriazole,
Mercapto oxadiazole, mercapto diazole,
Mention may be made of mercaptooxathiazole, tellurotetrazole or benzisodiazole. In a preferred embodiment, the inhibitor moiety or group is selected from the following chemical formulas:

[0193]

[Chemical 117]

In the above formula, R _I is a straight or branched chain alkyl, benzyl, phenyl and alkoxy group having 1 to about 8 carbon atoms and such a group containing no or at least one of these substituents. R _II is selected from R _I and —SR _I , R _III is a straight or branched chain alkyl group having 1 to about 5 carbon atoms, and m is 1 to 3. , And R _IV is hydrogen, halogen, an alkoxy group,
Phenyl group, carbonamido group, -COOR _V and -N
HCOOR _V, where R _V is selected from substituted and unsubstituted alkyl and aryl groups.

The coupler moiety contained in a development inhibitor releasing coupler is one which, although typically forming the image dye corresponding to the layer in which it is located, is combined with another film layer. Another color can also be formed as. It may also be useful for the coupler moiety contained in the development inhibitor releasing coupler to form a colorless product and / or a product washed out of the photographic material upon processing (so-called "universal" couplers). ).

As noted above, the development inhibitor releasing couplers can include the timing groups described above for the high dye yield couplers of this invention. Development inhibitor releasing couplers suitable for use in the present invention include, but are not limited to, the following compounds.

[0197]

[Chemical 118]

[0198]

[Chemical formula 119]

Research Disclosure
(November 1979, Item 18716, K, UK
enness mason publications
(Dudley Annex, 12a North Street, Emsworth, Hamps
hire, P010 7DQ), which is incorporated herein by reference), to obtain a reflective color print using the concepts of the present invention. It is possible that you can do it. The material of the present invention was prepared according to European Patent No. 5 on a pH adjusted support as described in US Pat. No. 4,917,994.
No. 4,346, with an epoxy solvent as described in EP 164,961 on a low oxygen permeable support such as described in US Pat. No. 4,346. , 165 and 4,540,6
US Pat. No. 4,994,359 for reducing the sensitivity to polyvalent cations such as calcium with nickel complex stabilizers as described in US Pat. No. 53 and 4,906,559. Can be applied with ballasted chelating agents as described in US Pat. No. 5,068,171 and with stain reducing compounds as described in US Pat. No. 5,068,171. Other compounds useful in combination with the present invention are disclosed in Japanese Patent Application Publication No. JP-A-A-B1 in the Abstract of England having the following accession numbers: 90
-72629, 90-72630, 90-72631,
90-72632, 90-72633, 90-7782
2, 90-78229, 90-78230, 90-79
336, 90-79337, 90-79338, 90-
79690, 90-79691, 90-80487, 9
0-80488, 90-80489, 90-8049
0, 90-80491, 90-80492, 90-80
494, 90-85928, 90-86669, 90-
86670, 90-87360, 90-87361, 9
0-87362, 90-87363, 90-8736
4, 90-88097, 90-93662, 90-93
663, 90-93664, 90-93665, 90-
93666, 90-93668, 90-94055, 9
0-94056, 90-103409, 83-6258
6 and 83-9959.

The emulsions particularly useful in this invention are tabular grain silver halide emulsions. Particularly contemplated tabular grain emulsions have a thickness of less than 0.3 .mu.m (for blue sensitive emulsions 0.
The tabular grains having an average tabularity (T) of more than 25 (preferably greater than 100) and an average tabularity (T) of less than 5 μm) account for more than 50% of the total projected area of the emulsion grains. Here, the term “flatness” is a term recognized in the technical field and is represented by the following formula: T = ECD / t ² . In the formula, ECD is the average equivalent circular diameter (μm) of the tabular grains, and t is the average thickness (μ) of the tabular grains.
m).

The average useful ECD of photographic emulsions can range up to about 10 μm, but in actual emulsions ECD's seldom exceed about 4 μm. ECD
Since both photographic speed and granularity increase with increasing .gamma., It is generally preferred to employ the smallest tabular grain ECD that does not interfere with achieving the desired speed requirements.

Emulsion tabularity increases markedly with reductions in tabular grain thickness. It is generally preferred that the target tabular grain projected area be accounted for by thin (t <0.2 μm) tabular grains. To achieve the lowest levels of granularity, it is preferred that the projected area of the tabular grains of interest be occupied by ultrathin (t <0.06 μm) tabular grains. The thickness of tabular grains is about 0.0
It is typically in the range of up to 2 μm. However, thinner tabular grain thicknesses are contemplated. For example,
U.S. Pat. No. 4,672,02 to Daubendiek et al.
No. 7 describes a tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 μm (iodide content 3 mol%). For ultrathin tabular grain high chloride emulsions,
It is described in Maskasky US Pat. No. 5,217,858.

As described above, tabular grains thinner than the specified thickness account for 50% or more of the total grain projected area of the emulsion. To maximize the benefits of high tabularity, it is generally preferred that tabular grains satisfying the thickness criteria above account for the highest conveniently achievable percentage of the total grain projected area of the emulsion. For example, in preferred emulsions tabular grains satisfying the thickness criteria above account for at least 70 percent of total grain projected area. In the tabular grain emulsion showing the highest performance, tabular grains satisfying the above-mentioned thickness standard are 9% of the total grain projected area.
It accounts for 0% or more.

Suitable tabular grain emulsions can be selected from among a variety of conventional teachings. Examples of such teachings include: Research Di
sclossure (Section 22534, 1983, 1)
Mon); U.S. Pat. Nos. 4,439,520 and 4,41.
No. 4,310, No. 4,433,048, No. 4,6
No. 43,966, No. 4,647,528, No. 4,
665, 012, 4,672, 027, 4,678, 745, 4,693, 964, 4,713, 320, 4, 722, 886,
No. 4,755,456, No. 4,775,617
No. 4,797,354, No. 4,801,52
No. 2, No. 4,806,461, No. 4,835,0
No. 95, No. 4,853,322, No. 4,914,
No. 014, No. 4,962, 015, No. 4,98
No. 5,350, No. 5,061,069 and No. 5,
061,616.

The silver chloride tabular grains useful in the present invention are {1
00} including grains having a major surface. These grains are morphologically stable and can be easily sensitized with various sensitizing dyes. A silver chloride emulsion suitable for the present invention is
Emulsion characterized by tabular grains defined by {100} major faces having an adjacent edge ratio of less than 10 and having aspect ratios of 2 or more each occupying 50% or more of the grain aggregate projected area. Is. For such emulsions, House et al., Approved US Patent Application No. 11
No. 2,489, Maskasky U.S. Pat. No. 5,264,337 and licensed U.S. Patent Application No. 035,349, which are hereby incorporated by reference. It will be adopted.

The emulsion may be a surface-sensitive emulsion, that is, an emulsion which forms a latent image mainly on the surface of silver halide grains, and the emulsion is preferentially internal latent image inside the silver halide grains. Images can also be formed. The emulsion may be a negative type emulsion, for example, a surface-sensitive emulsion or an unfogged internal latent image forming emulsion, and may be a positive type when it is subjected to uniform exposure or is developed in the presence of a nucleating agent. It may be a direct positive emulsion of an internal latent image forming type of fog.

The photographic element can be exposed to actinic radiation, which is typically in the visible region of the spectrum, to form a latent image, which can then be processed to form a visible dye image. it can. Processing to form a visible dye image includes the step of contacting the photographic element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developer in turn reacts with the coupler to form a dye.

With negative-working silver halide, the processing step described above provides a negative image. The above photographic elements are Th
e British Journal of Photo
ography Annual (1988, No. 191)
~ 198) and the known C-41 color process. If applicable, T
he British Journal of Pho
tography Annual (1988, 19th)
The element may be processed according to a color printing process such as the Eastman Kodak RA-4 process described at pages 8-199). To obtain a positive (or reverse) image, the exposed silver halide is developed without dye formation by development with a non-color developer prior to the color development step, then the element is uniformly fogged. The unexposed silver halide may be made developable. Alternatively, a direct positive emulsion can be used to obtain a positive image.

A preferable color developing agent is p-type as shown below.
Phenylenediamines: 4-amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N, N-diethylaniline hydrochloride,
4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N
-(Β-hydroxyethyl) aniline sulfate, 4
-Amino-3-β- (methanesulfonamido) ethyl-
N, N-diethylaniline hydrochloride, and 4-amino-N
-Ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid.

Usually, the developing step is followed by conventional steps such as bleaching, fixing or bleach-fixing for removing silver and silver halide, a washing step and a drying step.

Throughout the specification and claims, when identifying a substituent by a group containing a substitutable hydrogen (eg, alkyl, amine, aryl, alkoxy, heterocycle, etc.), especially It is to be understood that unless otherwise indicated, the unsubstituted forms of the substituents are included as well as the forms further substituted with any photographically useful substituents. Usually, such additional substituents will have less than 30, and typically less than 20, carbon atoms.

The couplers of this invention are described in US Pat.
It can be prepared by methods known in the art of organic synthesis, including those described in 0,884.

[0213]

Examples Synthesis of coupler Synthesis of coupler represented by the following formula

[0214]

[Chemical 120]

The overall route for coupler synthesis is described in Scheme I. Linking group intermediate 10 was synthesized in four steps. 2,6-lutidine (56 g, 0.52 mol, 60.
Commercially available methyl p-aminobenzoate (78.6 g, 0.52 mol) was dissolved in about 500 mL of methylene chloride containing 7 mL), cooled in an ice bath, and trifluoromethanesulfonic anhydride (146 g, methylene chloride). (0.52 mol / L in 50 mL) was added dropwise over 5 minutes. The reaction mixture was warmed to room temperature over 30 minutes and washed with excess 2N HCl. The organic phase was then washed 4 times with 250 mL portions of 1N NaHCO ₃ . The aqueous wash was acidified with 12N HCl to precipitate out a cream colored solid which was collected, washed with water and dried to give 86 g of trifluoromethylsulfonamide (p-trifluoromethylsulfonamide methyl benzoate). )was gotten. This trifluoromethylsulfonamide (86 g, 0.3 mol) was added to 660
A solution of NaOH (55 g, 1.38 mol) in mL of water was added with stirring. After stirring the mixture for about 15 minutes, it was acidified with excess 2N HCl to give a precipitate, which was collected, washed with water and dried.
72 g of saponified benzoic acid was obtained. This benzoic acid (7
4.9 g, 0.278 mol) was converted to the acid chloride by stirring in a mixture of 350 mL ethyl acetate, 3 drops DMF and 53 g (0.417 mol) oxalyl chloride for 3 hours. Let The solvent is removed by vacuum distillation,
The residual oxalyl chloride was then removed 3 times with a mixture of 150 mL methylene chloride and 50 mL heptane. The crude oil was mixed with 25 mL heptane and left in the refrigerator overnight. About 200 crystals formed
Slurry in mL of heptane and air dry to give 5
7.6 g of acid chloride was obtained. This acid chloride (57.
6 g, 0.198 mol in 100 mL of tetrahydrofuran) was added to 3-amino-4-hydroxybenzyl alcohol (27.27) in 100 mL of pyridine cooled to 5 ° C in a 3-neck round bottom flask equipped with a mechanical stirrer. 5
g, 0.198 mol) was added dropwise over 10 minutes with good stirring. After 30 minutes at room temperature, the reaction mixture was diluted with 300 mL ethyl acetate and an excess of 2 was added.
Wash with NH Cl and water. The organic layer was dried over MgSO ₄ and stripped to give a crude oil which crystallized immediately upon addition of 200 mL heptane. The crystals were collected and air dried to give 69 g of the bonding group 10.
was gotten. 32 g (0.082 mol) of 10 and 48.5 g (0.082 mol) of 11 are bonded to this bonding group 10.
Coupled to coupler 11 by combining with 00 mL DMF and treating with tetramethylguanidine (18.8 g, 0.164 mol). The reaction mixture was stirred for 2 hours then diluted with ethyl acetate and washed with excess 1N HCl and water. The organic layer is Mg
Dry over SO ₄ and concentrate to an oil. The oil was dissolved in 2 parts ethyl acetate and diluted with 8 parts heptane. Evaporation of these solvents with stirring gave brown crystals. These crystals were slurried in heptane, collected and air dried to give about 60 g of the desired coupler.

The dye intermediate 13 is represented by the scheme I shown below.
Synthesized according to I. In a round bottom flask equipped with a condenser and heating mantle, commercially available 2,5-dimethylaniline (50 g, 0.413 mol) was added to formic acid (46 g, 1 mol,
38 mL). The mixture was heated under reflux for 2 hours, cooled to room temperature, and then poured into 2 L of cold water while stirring well. The obtained precipitate was collected and air-dried to obtain 61 g of formamide (2,5-dimethylformanilide). This formamide (59.6 g,
0.4 mol) and bromodecane (104.6 g, 0.4 mol) were mixed with 40 mL t-butanol and 400 mL THF in a 3-neck round bottom flask equipped with a reflux condenser, heating mantle and nitrogen purge. . This mixture was treated with potassium t-butoxide (49.2 g) and
Heated at reflux for 2 hours, cooled to room temperature and diluted with ethyl acetate. This mixture is then treated with an excess of 1N H.
Wash with Cl and water. The organic layer was dried over MgSO ₄ and concentrated to give about 120 g of crude alkylated formamide. This alkylated formamide (120
g, 0.38 mol) to 420 mL acetic acid and 120 mL
Dissolved in 12N HCl and heated at reflux for 16 hours. The solvent was removed by vacuum distillation and the resulting solid was collected and air dried to give 107 g of the corresponding amine hydrochloride (2,5-dimethyl-N-dodecylaniline hydrochloride). This amine hydrochloride (34.2 g, 0.105
Mol) in a large 3 L round bottom flask equipped with mechanical stirrer and heating mantle with 250 mL of acetic acid and 20
Mix with 12 mL HCl with 20 mL formaldehyde. After heating the mixture to about 80 ° C.,
Remove heat and, with good stirring, add N, N in small portions
Treated with dimethylnitrosoaniline (22.5 g, 0.15 mol) for 10 minutes. The solvent was removed by vacuum distillation and the resulting oil was dissolved in 300 mL ethyl acetate and excess 2N HCl. The aqueous phase was washed 3 more times with 300 mL portions of ethyl acetate. After passing the silica gel pad through these ethyl acetate extracts, the solvent was removed under reduced pressure to obtain a slurry, to which 500 mL of heptane was added for crystallization. When these crystals were collected and air-dried, 17 g of aldehyde (2,5-dimethyl-4-
Dodecylamino-benzaldehyde; DMBA) was obtained.

In a 600 mL round bottom flask equipped with a mechanical stirrer, commercially available 4-t-butylphenol (30 g, 0.2 mol) was dissolved in 200 mL of acetic acid and the mixture was heated to 0 ° C.
Cooled down. To this mixture was added nitric acid (1 mL in 13 mL water).
3 mL) was added dropwise over 10 minutes, and then a catalytic amount of NaN
Treated with O ₂ . After 45 minutes, the reaction mixture was washed with excess 1N.
After washing with HCl and drying the organic layer with MgSO ₄ and stripping, 37 g of 2-nitro-4
-T-Butylphenol was obtained. This nitrophenol (37 g, 0.19 mol) was dissolved in 100 mL of ethyl acetate and a teaspoonful of 10% Pd was added.
/ C in Parr bottle. The mixture was placed on a hydrogenator at 3.4 × 10 ⁵ Pa (50 psi).
Under hydrogen for 1 hour with stirring. The catalyst was removed by filtration through Celite ™ and the ethyl acetate stripped under reduced pressure. 25.6 g of the corresponding amine (2-amino-4-t-butylphenol) was obtained from the material crystallized by adding about 200 mL of heptane.

In a 1 L 3-neck round bottom flask equipped with an ice bath and addition funnel, methanol (38 g, 1.2 mol, 48
(mL) and 200 mL of methyl formate, malononitrile (39.6 g, 0.6 mol) was dissolved. The mixture was cooled to 10 ° C. and thionyl chloride (55 g, 0.
46 mol, 33.6 mL) was added dropwise over 5 minutes. Three
A precipitate formed after 0 minutes and an additional 100 mL of methyl formate was added. After 1 hour, collect the precipitate and collect 2
Air dried for 0 minutes, yielding 52 g of the corresponding imine salt intermediate 14. The salt was stored in a nitrogen-purged airtight bottle. This imine salt (10.7g, 0.0
8 mol) and 2-amino-4-t-butylphenol (6.6 g, 0.04 mol) were heated with 100 mL of methanol at 60 ° C. for 10 minutes and then diluted with 200 mL of ethyl acetate and excess water. This organic layer is Mg
After drying over SO ₄ and stripping, 8.6 g of benzoxazole 15 was obtained. This oil (4.5
g, 0.02 mol), aldehyde DMBA (6.7 g, 0.02 mol) in 80 mL of acetic acid, and 3 drops of triethylamine were heated at 80 ° C. for 15 minutes and then stirred at room temperature overnight. To obtain a slurry-like crystal. When the crystals were collected and washed with 100 mL of methanol, there were two crops containing about 7 g of methine dye 16. This dye (3.5 g, 0.0068 mol) was dissolved in about 25 mL of methylene chloride and 2,6-lutidine (1.9 g, 0.017 mol). This mixture was treated with phosgene (1.93 M in toluene, 0.014 mol, 7.2 mL) over 1 minute. After 10 minutes, the mixture was washed with excess cold 1N HCl in a separatory funnel followed by cold water. The organic phase was dried over MgSO ₄ and stripped to give 3.7 g of carbamoyl chloride 13. After scale-up, a nitrogen purge was provided and dimethylaminopyridine (3.
This carbamoyl chloride (17.9 g, 0.031 mol) was added to coupler 1 in a 1 L 3-neck round bottom flask containing 8 g, 0.031 mol) and 150 mL methylene chloride.
Reacted with 2 (29.3 g, 0.131 mol). The mixture was treated with DBU (14.1 g, 0.093 mol), stirred for 4 hours, diluted with ethyl acetate and washed with excess 1N HCl and water. The organic layer is MgSO ₄
Dried over and concentrated to a crude oil which was eluted with methylene chloride / heptane / ethyl acetate (5/3/2).
Silica gel chromatography using. About 2
0.5 g of the inventive coupler was obtained in the form of a foam.

[0219]

[Chemical 121]

[0220]

[Chemical formula 122]

Photographic Examples Example 1 Two emulsions, Emulsion A (15 mol% iodide, 2.1 μm)
m, saturated iodide core, silver bromoiodide emulsion) and Emulsion B (15 mol% iodide, 2.1 μm, saturated iodide core, silver bromoiodide emulsion) along with image coupler C-1 (control) and Inv. The invention is illustrated by the following results from a monochrome coating experiment with -1 and Inv-2 (invention) applied. Although the grain size of the emulsion was the same, the concentration (Dmin) in the unexposed area was lowered by adding an additive to Emulsion B at the time of finishing. The high dye yield image coupler, Inv-1, and Inv-2 were coated at half the molar amount of the comparative conventional C-1 coupler.

The coating format for the monochrome yellow format coated on the REMJET film base was as follows. Layer 1: Silver bromoiodide (15 mol% I, 1.29 g / m ²
Ag), a common image coupler Comp-1 (0.36
mM / m ² ) or coupler with high dye yield (0.18 m
An emulsion layer containing M / m ² ), gelatin (2.69 g / m ² ) and a diffusing agent (1.0% by weight of the melt). Layer 2: Gelatin (1.29 g / m ² ), 1,1 ′-(methylenebis-sulfonyl) bis-ethane hardener (1.75% of total gelatin) and diffusing agent (1.0 of melt weight).
Wt%) overcoat layer.

Image couplers with high dye yield are di-n-
It was provided as a 2: 1 weight ratio dispersion in butyl phthalate. The conventional image coupler Comp-1 was provided as a dispersion free of permanent coupler solvent. The chemical formulas of the couplers used in the test are shown below.

[0224]

[Chemical 123]

[0225]

[Chemical formula 124]

The coatings were exposed to blue light with a step wedge having a density gradient and processed using the Kodak Flexicolor C-41 ™ protocol. Sensitometric parameters are obtained,
See the table below. Speed refers to the exposure amount at which the density on Dmin in the D / logE curve is 20% of the average gradation from the exposure amount at Dmin to the exposure amount 0.61 logE higher than Dmin. Inertia sensitivity is D
The exposure dose determined by the point where the line showing the maximum slope of the / logE curve intersects the Dmin density line.

[0227]

[Table 1]

Comparing coatings # 1 and # 4 (low Dmin) shows that the speeds are in harmony, but the contrast of coating 1 is considerably (31%) higher. The Dmin of coating 4 was 0.05 lower than that of coating 1. These data explain the difference between the two emulsions when coated with the same conventional image coupler. Emulsion B has a lower Dmin and lower contrast.

Coating Nos. 5 and 6 showed comparable contrast to Coating 1, but the increase in Dmin was very modest. More importantly, the highly desirable result, a significant speed increase, was more than enough to compensate for the increase in Dmin. Thus, when the high dye yield couplers of this invention were used in combination with Emulsion B, a significantly higher speed point than the conventional system was achieved with a slight increase in Dmin.

When the high dye yield couplers of this invention were combined with the more developable, more highly finished Emulsion A, ie coatings # 2 and # 3, the speed was increased over coating # 1 ( However, although not as good as Coatings 5 and 6) and comparable contrast was achieved, the Dmin values were also very high. This illustrates the improvement obtained by using a combination of a low developability emulsion B and a high dye yield coupler.

The above examples are intended to illustrate particular embodiments of the invention and are not intended to limit the scope of the materials or combinations of the invention. Further embodiments and advantages within the scope of the claims will be apparent to those skilled in the art. The patent specifications, publications, and applications filed on the same day and the co-pending patent applications cited herein are incorporated herein by reference in their entirety.

The preferred embodiments of the present invention will be described below item by item. (1) A support bearing at least one photographic silver halide emulsion in combination with at least one dye-rich coupler releasing an electrically neutral dye chromophore or dye precursor. A photographic element in which the emulsion exhibits low developability. (2) The coupler having a high dye yield can react with an oxidized product of a color developer to form a yellow dye (1).
Elements described in the section. (3) The element according to item (1), wherein the coupler having a high dye yield is a coupler that releases a dye (or a dye precursor) containing a methine, an azamethine, or an azo group. (4) The element according to item (1), wherein the coupler having a high dye yield is a coupler in which the dye formed from the released dye or the dye precursor exhibits yellow.

(5) The released dye or the dye formed from the dye precursor is -OC (O)-, -OC (S)-,
-SC (O)-, -SC (S)-and -OC (= NSO
₂ R)-, where R is an alkyl or aryl group which may or may not be substituted, and which has an electrically neutral dye chromophore bonded to a linking group selected from the group consisting of: The element according to item (1). (6) The coupler having a high dye yield has the following formula: COUP- (T) _m -L-DYE (where COUP is the first dye which reacts with the oxidized color developing agent at the coupling site). Is a base group of a coupler capable of producing a silane, T is one or more timing groups in which m is an optional component of 0 to 2, L is a linking group, and DYE is a second dye. Is shown),
The element according to item (1). (7) L is -OC (O)-, -OC (S)-, -SC
(O) -, - SC ( S) - and -OC (= NSO ₂ R)
-Wherein R is an alkyl or aryl group which may or may not be substituted),
The element according to item (6). (8) m is 1 or 2, and at least one T
Each independently includes a bond from COUP or another timing group to an oxygen atom, which oxygen atom is optionally substituted with one or two of the optionally substituted hydrocarbyl or heterocyclic ring. A ring-bonded methyl group which may be substituted with 4 alkyl groups is bonded to a position capable of being conjugated, and this methyl group is bonded to an L-DYE group or a second timing group, (6) Elements described in the section. (9) At least one T is the following formula:

[0234]

[Chemical 125]

[In the above formula, Z is selected from the group consisting of nitro, cyano, alkylsulfonyl, sulfamoyl (-SO ₂ NR ₂ ) and sulfonamide (-NRSO ₂ R) groups, and R is hydrogen or alkyl. R is a substituent
^I , R ¹¹ and R ¹² are each independently hydrogen or a substituent that does not adversely affect the properties of the coupling reaction, the release reaction or the dye produced thereby.
The element according to item (6). (10) The element according to item (6), wherein COUP is an open chain ketomethylene compound capable of forming a yellow dye when reacted with an oxidized product of a developer. (11) When DYE or DYE is a dye precursor, the dye produced from DYE is selected from the following,
The element according to item (6). Azo dye moiety containing -NR ¹ -group represented by the following structural formula

[0236]

[Chemical formula 126]

Wherein R ²⁵ is hydrogen or a substituent such as alkyl, and R ²⁶ and R ²⁷ each independently represent hydrogen or one or more substituents such as alkyl. Azamethine dye moiety containing -NR ¹ -group represented by structural formula

[0238]

[Chemical 127]

Wherein R ²⁸ is hydrogen or one or more substituents, eg alkyl, R ²⁹ is hydrogen or a substituent such as alkyl, and EWG is an electron withdrawing group. A methine dye moiety containing a —NR ¹ — group represented by the following structural formula

[0240]

[Chemical 128]

Wherein R ³⁰ and R ³¹ are each independently hydrogen or a substituent such as alkyl, R ^30a is hydrogen or one or more substituents such as alkyl, and E
WG is an electron-withdrawing group with a positive Hammett sigma (para) value).

(12) The silver iodide content of the emulsion is 6 mol% or more of the total silver halide present in the layer, and the average grain size of the emulsion is 1.5 μm or more. (1) Elements described in the section. (13) The silver iodide content of the emulsion is 6 mol% or more of the total silver halide present in the layer, and the average grain size of the emulsion is 1.5 μm or more. Elements.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Robert James New Mirror New York, USA 14612, Rochester, Long Pond Road 31

Claims (1)

[Claims] 1. Carrying at least one photographic silver halide emulsion in combination with at least one high dye yield coupler releasing a dye or dye precursor having an electrically neutral dye chromophore. A photographic element containing a support in which the emulsion exhibits low developability.